Copper fungicides and process of producing same



'C22ZA r i i i 1 COPPER FUNGICIDES AND PROCESS OF PRODUCING SAMEAlexander A. Nikitin, Copperhill, Tenn., assignor to Tennessee CopperCompany, New York, N. Y., a corporation of New Jersey No Drawing.Application June 21,1942, Serial No. 448,846

9 Claims.- (Cl. 260--113) i This invention relates to fungicides andcomprises a new and useful fungicide and the process of making the same.

Fungicides are well known in which copper enters as an element such, forexample, as Bordeaux mixtures. When a fungicide is sprayed on a crop itshould be uniformly and evenly distributed over the entire surface ofthe crop t be efiective and should efficiently adhere thereto, shouldstand what is called weathering, and should be free from any injuriouseffect upon the crop. All fungicides with which I am'familiar and inwhich copper enters as an active ingredient are lacking in one or moreof these essentials. Furthermore, some of the fungicides are composed ofa plurality of constituents which have to be mixed by an attendant whenthey are applied to the crop, and unless they are mixed in properproportions and in the proper way their efiiciency i reduced if notdestroyed. They are undesirable for this reason.

Repeated attempts have been made with slight success to improve thephysical properties of basic copper sulphate by the addition ofsupplementary materials such as vegetable flour. The addition of thealkali salts of the protein substances such as calcium caseinate helpedto improve the covering properties of basic copper sulphate but it wasfound that the adherence of the spray residue of the copper fungicideswas greatly reduced. The protein substances such as casein or soya flourby themselves did not improve the spreading properties since it was verydiflicult to disperse them in water without the addition of alkali. Itshould be emphasized that thedeleterious action of alkali was notconfined to the poor adherence only but it also rendered basic coppersulphate incompatible with organic insecticides, such as derris orpyrethrum. Further the handling of these protein substances for sprayapplication required skill and knowledge not possessed by th averagefarmer.

The effort to introduce the protein substances such as casein failedwhen the casein was used without excessive amount of alkali since thefinal product wasnot readily wettable.

The Present invention has for its object to provide a fungicide in whichcopper enters as an effective ingredient, which has highly toxicproperties; which is chemically stable in the presence of alkalies suchas lime and which is stable upon exposure to atmospheric action; whichis readily wettable, and has goodspreading and adhering properties,which is free of injuriou effects on the crop, and which is ready to beapplied to the crop by dusting or by merely dispersing the same in asuitable amount of water.

It was fo undlh at when a splption of a copper mino-sulphate proteinate.

em d nra i nieu a is ented MEE alkali miil iiffiieneis or soaps of thefatty acids, the resultant r opper alumino compoi'1ifdpos sesses greatlyimproved y ica propeniesisucm:asrtsprea neilhiieliiiie a d eesieaias"rinse new copper'fungicides are coppg; 3 111 mino salts in whichthealygpinug is present in the 'form ofaluifiifiuiiijhydrate as hasbeenprpved by l'ie'i'fiifiaT'aTnalyses. The soyab ean protein orsoapsofjfatty acids is combined wit through the'aid"Eiftlie'aliiinifiito form the new compound which possesses greatly improvedphysical and chemical properties. The new copper fungicides arest'ablechemically when they are exposed to atmospheric. action. They arecompatible with lime and lead arsenate plus lime. They are alsocompatible with oil emulsions and with organic insecticides such aspyrethrum and rotenone. They also retain their neutral character inwater suspension, and during storage.

The procedure which is followed in the preparation of the improvedfungicide involves dissolving a copper salt in water with an aluminumsalt, which is for convenience designated solution A.

I then introduce into a suitable amount of Water a protein-containingmaterial preferably soya bean flour (about 50% protein) or soaps of afatty acid such as oleic, stearic or lino-leic, together with an alkalisuch as ammonium hydroxide. This for convenience I designate solution B.

I then add solution B to solution A until the resulting slurry isapproximately neutral (pl-I 6.8-6.9) thereby precipitating a basiccopper alu- This precipitate is filtered and the filter cake i reducedto a finely divided powder, and it is then ready for use.- This finelydivided basic copper alumino-sulphate proteinate may be dusted on thecrop or may be dispersed in water at various concentrations dependingupon the crop and the extent of the fungus infection on the crop.

In making solution A the proportions of copper salt and aluminum saltemployed may be varied, depending upon the amount of protein or soaps offatty acids that are used. Thus, 30 part of the aluminum sulphate(A12(SO4)3.12H2O) may be added to parts copper sulphate (CllSO4.5H2O) orthe amount of aluminum sulphate may be decreased to any desired extentdown to 5 parts of aluminum sulphate to 100 parts of copper sulphate.

In making solution B the concentration may be varied according to thecharacter of the alkali used, since the amount of alkali used willdepend until complete precipitation takes place at about pH 6.8, whichpH should not be substantially departed from in order to avoid theformation of soluble cupro ammonium compounds which form with-an excessof ammonia. Ifthe pH of the slurry is'carried beyond that point thecomplete precipitation of the components will not be secured.

For the purpose of illustrating one embodiment of the inventive ideareference is made to the following example, but it is to be expresslyunderstood that the invention is not limited to this specific example.The choice of the copper salt and aluminum salt to be used in solution Amay be varied. The proportions of aluminum sulphate may be variedanywhere within 5% to approximately 30% of the copper sulphate employed.This gives from 1% to alumina (A1203) in the finishedproduct. Moreoverany protein-bearing material,.whether vegetable or animal, as well assoaps of fatty acids may be employed and the percentage thereof varied.However, the amount of protein material in solution B should be such asto give from 0.5 to 3.5% protein in the finished product.

As an example, dissolve in water 100 grams of copper sulphate and gramsof aluminum .sulphate thus forming solution A. Then dissolve 1 to 7grams of soya bean flour and grams of ammonium hydroxide about 25% ofNE; in water, thus forming solution B. Then add solution B to solution Auntil the resulting slurry reaches a pH of approximately 6.8, thenfilter the resulting precipitate and reduce it to a fine powder.

I discovered thatwhenthe aluminum anigp p:

per salts were precipitated in one onerati or t soapof yratty aisiathey"itrm gggdbp f alumin'o conipound' whichfurnished a higheramountfofsoluble copper and consegue tl more effec we in. the contrcopper fungicides when in water suspension forms about 1.5 parts permillion of soluble copper, which is not sufficient for theeffective'control .of

' fungus disease, .The amount of soluble copper is increased-by the useof soya flour protein to about 24.5 parts per million.. This is superiorto calcium caseinate which increases the amount of soluble copper to103.6 parts per million but it has such an inferior tenacity coefficientthat soya bean protein is superior in performance..

It was noted that when a copper sulphate s olu .analuminum salt isprecipitated with copper sulphate, the resultant copper compound isreadily wettable.

The orientation of the molecules .in the surfaces is a material factorin the wetting of the soya bean protein or the soaps of the fatty acidswhich are introduced intothe copper fungicides. Apparently thehydrophylic. or friendly-to-water ends of the fatty acid molecules whenthey are precipitatedin combination with the aluminum salt, are turnedoutward inv the surface in such. condition that they are easily wettableby water, while the hydrophobic or greasy ends are turned inward in thesurface.

Y When a soluble aluminum salt is added to the copper sulphate solutionand then.precipitated pro L with an alkali .,solution containing soyabean protein, or the soaps of fatty acids; the resultant coppercompounds, such as copper alumino-carbonate and basic copperalumino-sulphate containing soya bean protein or soaps of fatty acidsshow greatly improved spreading and adherence properties. When analuminum salt and copper sulphate solution are co-precipitated with analkali free from soya bean protein or soaps of fatty acids, theresultant copper compound does not show any improvement in spreadingproperties. The best spreading and sticking properties are obtained onlywhen soya bean protein and a soluble aluminum salt are introduced intothe reagents before the precipitation of the copper compound has takenplace. .Barticularly good results were secured. in. spore germinationtests and in the spray field in the control of..bitter rot on. appleswith basic copper alumino-sulphate .proteinate.

The copper fungicides of the present invention possess superior toxicityor killing power to basic copper sulphate as shown by tests on culturesuspension of Macrosporiumv soZam' and Glomerella. cinoulata spores,asfollows:

Per cent spor Dilution P germination equivaor 2%? Material lent to centBordeaux Cu Macro- Glommixture sporium erella solani cingulata Check 8789 1 Basic copper sul- 0. 50-50 0 030 34 28 phate. 2 .do'. 1. 00-50 060,21 l7 3 do 1. 50-50 090 10 8 4 Basic oopper- 050-50 .030 20 '17alumino-sulphatcproteinate. 5 do 1. 00-50 050 ll 3 6 .do 1. 50-50 000 32 The same advantages of the copper fungicides of the present inventionwere shown by extensive field tests that demonstrated'vastly superiorcontrol of fungus diseases, as proved by'increased yield of celery cropswhich are extremely sensitive to blight infection. This was in contrastto regular basic copper sulphate.

It is again emphasized that the spreading and adhesive properties of thenew copper fungicide are superior to those of either the regular basiscopper sulphate compounds or the compounds of copper and aluminumwithout protein. This is of great importance in order to insurecompleteness of contact between the pathogenic organism and the sprayresidue and especially so when used on glossy citrus leaves. Furtherthese improved fungicides are readily dispersed in water and they willremain in suspension without the addition of an auxiliary dispersingagent.

The new copper fungicides have a much higher chemical stability whenused in connection with insecticides such as arsenical compounds,pyrethrum and rotenone. When commonly available basic copper sulphatesare used with arsenical compounds in a spray mixture it is required thatlime should be used to reduce arsenicaliin} jury. The use of lime inthis case reduces the effectiveness of the copper, fungicide due tochemical interaction with the copper fungicidewhich has a tendencytodecomposeas shown .liyits blackening, when it is in water suspension'incombination with arsenicalsplus lime. On..the other hand, the new copperfungicide being corn.- patible with lime and arsenicals and thefungicide l i i may be used. V

H 'animal proteins, the present application and no protein is presentthe adherence of the resultant basic copper alumino-sulphate or copperalumino-carbonate is reduced.

When the A1203 content is in a range between 1 and 10%, and the soyabean protein or soaps of fatty acids is in a range between 0.5 and 3.5%on the basis of the finalproduct, the chemical stability and thephysical properties, such as dispersing, spreading and sticking, aregreatly improved as compared with regular basic copper sulphate, coppercarbonate, or copper alumino compounds without protein. When no aluminais present the resultant basic copper sulphate or copper carbonatecontaining protein is repellent to water. This is especially true whenthe protein content of the compound is above 1%. On the other hand, whena mixture of copper sulphate and aluminum sulphate is precipitated withan alkali containing soya bean protein or soaps of fatty acids, theresultant basic copper alumina-sulphate or copper alumino-carbonate isreadily wettable by water. The presence of the alumina group changes theproperties of the resultant copper compound in the presence of theprotein group from hydrophobic to hydrophylic. v

While I prefer the use of COPIQQLjl1Pha1B.finfl uminiunsu hate andsoraheaniisuxieai monia, it is to be understood that the invent'iohimum" inventive idea is susce rnbpdiments within' tfilimitsb fft opb tsei uirh'm' used in place oicoppe v ,7 2w suipheigmaintaieinei remaininCuO and AlzOgi r in place of aluminum, salts of zinc" may b used.Furthrthe alkali'iisdmlay be eithery l ati le such as ammonium hydrxideffifi ch as}; e bases of sodiu'rmpota um,

of the pie;

- 63a bean fi our which contaiiisfabout While I have described hereinthe soaps of the fatty acids as alternatives for the vegetable andclaims are limited to the copper-alumino-protein species, the speciesembodying the soaps of the fatty acids being made the subject matter ofa divisional application.

What is claimed is:

l. The process of manufacturing copper fungicides which comprisesreacting an aqueous solution of, copper and aluminum compounds selectedirom'the group consisting of copper sulphate and copper r carbonate andaluminum sulphate and 7 6 and precipitating a basic coppersalt-aluminaproteinate.

2. The process of manufacturing copper fungicides which comprises thereacting of an aqueous solution of copper and aluminum compoundsselected from the group consisting of copper sulphate and coppercarbonate and aluminum sulphate and aluminum oxide with an alkali and aprotein, the alkali and protein being added to the solution until the pHof the mixture becomes approximately neutral, and precipitating a basiccopper salt-alumina-proteinate.

3. The process of manufacturing copper fungicides which comprisespreparing an aqueous solution of copper and aluminum compounds selectedfrom the group consisting of copper sulphate and copper carbonate andaluminum sulphate and aluminum oxide, preparing an aqueou solution.

containing an alkali and a protein selected from the group consisting ofcasein, soya flour, skim milk and Wheat flour, reacting the twosolutions by mixing them together until the pH of the mixture becomesapproximately neutral, and precipitating a basic coppersalt-alumina-proteinate.

4. The process of manufacturing copper fungicides which comprisespreparing an aqueous solution of copper and aluminum compounds selectedfrom the group consisting of copper sulphate and copper carbonate andaluminum sulphate and aluminum oxide, preparing an aqueous solutioncontaining an alkali and a protein, reacting the two solutions by mixingthem together until the pH of the mixture becomes approximately neutral,and precipitating a basic copper salt-alumina-proteinate.

5. The process of producing a copper fungicide which comprises reactingan aqueous solution of copper and aluminum compounds selected from thegroup consisting of copper sulphate and copper carbonate and aluminumsulphate and aluminum oxide with ammonium hydroxide and soya beanprotein, the alkali and protein being added to the solution until the pHof the mixture becomes approximately neutral, and precipitating a basiccopper salt-alumina-proteinate.

6. The process of producing a copper fungicide which comprises preparingan aqueous solution of copper and aluminum compounds selected from thegroup consisting of copper sulphate and copper carbonate and aluminumsulphate and aluminum oxide, preparing an aqueous solution containingammonium hydroxide and soya bean protein, reacting the two solutions bymixing them together until the pH becomes approximately neutral, andprecipitating a basic copper salt-alumina-proteinate.

'7. As a new fungicide product a basic copper salt-alumina-proteinate inwhich the copp r salt is selected from the group consisting of coppersulphate and copper carbonate.

8. As a new fungicide product a basic copper salt-alumina-proteinate inwhich the copper salt is selected from the group consisting of coppersulphate and copper carbonate the alumina content being in the rangebetween 1% and 10% and the protein content being in the range between0.5% and 3.5%.

9. As a new fungicide product a basic copper salt-alumina-proteinate inwhich the copper salt is selected from the group consisting of coppersulphate and copper carbonate and the protein is selected from the groupconsisting of casein. soya flour, skim milk and wheat flour.

ALEXANDERA. NIKITIN.

Disclaimer 2,414,660.-Alemnder A. Nz'kz'tin, Copperhill, Tenn? COPPERFUNGwmEs AND PnocEss 0F PRODUCING SAME. Patent dated Jan. 21, 1947.Disclaimer filed. Mar. 29, 1948, by the assignee, Tennessee CopperCompany. Hereby enters this disclaimer to the words and. coppercarbonatg iii lines 4 and 5 of claims 1, 3, 4, 5, and 6, and line 5 ofclaim 2.

[Ofiicial Gazette May 4, 1948.]

Disclaimer 2,414,660.-Alexander A. Nz'kz'tz'n, Copperhill, Tenn? COPPERFUNGICIDES AND PRocEss OF PRODUCING SAME. Patent dated Jan. 21, 1947.Disclaimer filed Mar. 29, 1948, by the assignee, Tennessee CopperCompany. f Hereby enters this disclaimer to the w0rds and coppercarbonatq in lines4 and 5 of claims 1, 3, 4, 5, and 6, and line 5 ofclaun 2.

[Ofiicial Gazette May 4, 1948.]

